Relative contributions of crust and mantle to generation of Campanian high-K calc-alkaline I-type granitoids in a subduction setting, with special reference to the Harşit Pluton, Eastern Turkey

We present elemental and Sr–Nd–Pb isotopic data for the magmatic suite (~79 Ma) of the Harşit pluton, from the Eastern Pontides (NE Turkey), with the aim of determining its magma source and geodynamic evolution. The pluton comprises granite, granodiorite, tonalite and minor diorite (SiO₂ = 59.43–76.95 wt%), with only minor gabbroic diorite mafic microgranular enclaves in composition (SiO₂ = 54.95–56.32 wt%), and exhibits low Mg# (<46). All samples show a high-K calc-alkaline differentiation trend and I-type features. The chondrite-normalized REE patterns are fractionated [(La/Yb) _n  = 2.40–12.44] and display weak Eu anomalies (Eu/Eu* = 0.30–0.76). The rocks are characterized by enrichment of LILE and depletion of HFSE. The Harşit host rocks have weak concave-upward REE patterns, suggesting that amphibole and garnet played a significant role in their generation during magma segregation. The host rocks and their enclaves are isotopically indistinguishable. Sr–Nd isotopic data for all of the samples display I _Sr = 0.70676–0.70708, ε _Nd(79 Ma) = −4.4 to −3.3, with T _DM = 1.09–1.36 Ga. The lead isotopic ratios are (²⁰⁶Pb/²⁰⁴Pb) = 18.79–18.87, (²⁰⁷Pb/²⁰⁴Pb) = 15.59–15.61 and (²⁰⁸Pb/²⁰⁴Pb) = 38.71–38.83. These geochemical data rule out pure crustal-derived magma genesis in a post-collision extensional stage and suggest mixed-origin magma generation in a subduction setting. The melting that generated these high-K granitoidic rocks may have resulted from the upper Cretaceous subduction of the Izmir–Ankara–Erzincan oceanic slab beneath the Eurasian block in the region. The back-arc extensional events would have caused melting of the enriched subcontinental lithospheric mantle and formed mafic magma. The underplating of the lower crust by mafic magmas would have played a significant role in the generation of high-K magma. Thus, a thermal anomaly induced by underplated basic magma into a hot crust would have caused partial melting in the lower part of the crust. In this scenario, the lithospheric mantle-derived basaltic melt first mixed with granitic magma of crustal origin at depth. Then, the melts, which subsequently underwent a fractional crystallization and crustal assimilation processes, could ascend to shallower crustal levels to generate a variety of rock types ranging from diorite to granite. Sr–Nd isotope modeling shows that the generation of these magmas involved ~65–75% of the lower crustal-derived melt and ~25–35% of subcontinental lithospheric mantle. Further, geochemical data and the Ar–Ar plateau age on hornblende, combined with regional studies, imply that the Harşit pluton formed in a subduction setting and that the back-arc extensional period started by least ~79 Ma in the Eastern Pontides.     

Re–Os age of non-mineralized black shale from the Kupferschiefer, Poland, and implications for metal enrichment

Six samples of non-mineralized black shale from a Kupferschiefer section in the northern part of the Polish Zechstein Basin (Zdrada IG-8 drill hole: 1026.16–1026.90 m) were studied for Re–Os isotopes and selected major and trace elements. These black shales, averaging 5.82 wt.% C_org and 1.69 wt.% S_tot, display very low base metal values (up to 106 ppb Cu, 792 ppb Pb, and 144 ppb Zn) and have abundances of 64–1376 ppb Re and 0.37–1.25 ppb Os, with a ¹⁸⁷Os/¹⁸⁸Os ratio of 6.95–22.5. The regression of all Re–Os data yields an age of 247 ± 20 Ma, which is within the range of uncertainties of previous Rb–Sr and K–Ar geochronological studies. The scatter in the Re–Os data can be explained in terms of fluctuations in sedimentary conditions, i.e., restricted basin with terrestrial influence.     

Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Integrated stratigraphy and 40Ar/39Ar chronology of the early to middle Miocene Upper Freshwater Molasse in western Bavaria (Germany)

A detailed integrated stratigraphic study (biostratigraphy and magnetostratigraphy) was carried out on five sections from the western part of the Bavarian Upper Freshwater Molasse of the North Alpine Foreland Basin (NAFB), greatly improving the chronostratigraphy of these sediments. The sections belong to the lithostratigraphic units Limnische Untere Serie (UL) and Fluviatile Untere Serie (UF) and contain 19 (mostly new) small-mammal bearing levels, significantly refining the local biostratigraphy. Radiometric ages obtained from glass shards from tuff horizons are used together with the biostratigraphic information for constructing and confirming the magnetostratigraphic correlation of the studied sections to the Astronomical Tuned Time Scale (ANTS04; Lourens et al. in Geologic Time Scale 2004, Cambridge University Press, 2004). This correlation implies that the UL lithostratigraphic unit corresponds to the latest Ottnangian and the Early Karpatian, whereas the UF corresponds to the Karpatian and the Early Badenian. This indicates that the Brackish- to Freshwater Molasse transition already occurred during the late Ottnangian. The pre-Riesian hiatus occurred in the latest Karpatian and lower Early Badenian in Eastern Bavaria and Bohemia and in the Late Karpatian and earliest Badenian in Western Bavaria. The geochemical and Ar–Ar data of volcanic ashes suggest that highly evolved silicic magmas from a single volcano or volcanic center, characterized by a uniform Nd isotopic composition, erupted repetitively over the course of at least 1.6 Myr. Three phases of eruptive activity were identified at 16.1 ± 0.2 Ma (Zahling-2), 15.6 ± 0.4 Ma (Krumbad), and 14.5 ± 0.2 Ma (Heilsberg, Hegau). The correlation of the local biostratigraphic zonation to the ANTS04 enables further the characterization of both the Ottnangian–Karpatian and Karpatian–Badenian boundaries in the NAFB by small-mammal biostratigraphy. According to these results the Ottnangian–Karpatian boundary is contemporaneous with the first appearance datum of Megacricetodon bavaricus (in the size of the type population) and the first common occurrence of Keramidomys thaleri, whereas Ligerimys florancei, Melissiodon dominans and Prodeinotherium aff. bavaricum have been already disappeared during the late Ottnangian. The Karpatian–Badenian boundary is characterized by a significant size increase of the large Megacricetodon lineage and possibly a (re-)immigration of Prodeinotherium bavaricum.     

Timing of Holocene sand accumulation along the coast of central and SE Vietnam

In Vietnam, the coastal sand barriers and dunes located in front of the steep slopes of the high rising Truong Son Mountains are sensitive to climate and environment change and give evidence for Holocene sea-level rise. The outer barrier sands were deposited shortly before or contemporaneous with the local sea-level high stand along the Van Phong Bay postdating the last glacial maximum (LGM). Optically stimulated luminescence (OSL) dating yielded deposition ages ranging from 8.3 ± 0.6 to 6.2 ± 0.3 ka for the stratigraphically oldest exposed barrier sands. Further periods of sand accumulation took place between 2.7 and 2.5 ka and between 0.7 and 0.5 ka. The youngest period of sand mobilisation was dated to 0.2 ± 0.01 ka and is most likely related to reworked sand from mining activities. At the Suoi Tien section in southern central Vietnam, the deposition of the inner barrier sands very likely correlate with an earlier sea-level high stand prior to the last glaciation. OSL age estimates range from 276 ± 17 to 139 ± 15 ka. OSL dating significantly improves our knowledge about the sedimentary dynamics along the coast of Vietnam during the Holocene.     

Adjoint formulation and constraint handling for gradient-based optimization of compositional reservoir flow

An adjoint formulation for the gradient-based optimization of oil–gas compositional reservoir simulation problems is presented. The method is implemented within an automatic differentiation-based compositional flow simulator (Stanford’s Automatic Differentiation-based General Purpose Research Simulator, AD-GPRS). The development of adjoint procedures for general compositional problems is much more challenging than for oil–water problems due to the increased complexity of the code and the underlying physics. The treatment of nonlinear constraints, an example of which is a maximum gas rate specification in injection or production wells, when the control variables are well bottom-hole pressures, poses a particular challenge. Two approaches for handling these constraints are presented—a formal treatment within the optimizer and a simpler heuristic treatment in the forward model. The relationship between discrete and continuous adjoint formulations is also elucidated. Results for four example cases of increasing complexity are presented. Improvements in the objective function (cumulative oil produced) relative to reference solutions range from 4.2 to 11.6 %. The heuristic treatment of nonlinear constraints is shown to offer a cost-effective means for obtaining feasible solutions, which are, in some cases, better than those obtained using the formal constraint handling procedure.     

Responses of microorganisms and enzymes to soil contamination with metazachlor

A greenhouse pot experiment was conducted at the University of Warmia and Mazury in Olsztyn, with the aim of describing the influence of metazachlor on counts and biodiversity of soil microorganisms, soil enzymatic activity, physicochemical properties of soil and yield of spring oilseed rape. The first experimental factor was soil contamination with increasing rates of metazachlor: 0 (soil without the herbicide), 0.333 (recommended by the manufacturer), 6.666, 13.332, 26.665, 53.328, 106.656 and 213.312 mg kg^?1 dm of soil, while the second factor comprised two dates of determination: 30 and 60 days after starting the experiment. The tested herbicide had an adverse effect on reproduction of all analyzed microorganisms: oligotrophic bacteria and their endospore forms, Azotobacter spp. bacteria, organotrophic bacteria, actinomycetes and fungi. The values of the colony development and eco-physiological diversity indices decreased under the influence of excessive doses of the herbicide. Also, significant fluctuation in the enzymatic activity of soil was observed in response to the higher doses of metazachlor and depending on the date of determinations. The herbicide had an invariably negative influence on the activity of soil enzymes, causing the inhibition of dehydrogenases, catalase, urease, acid phosphatase, alkaline phosphatase, arylsulfatase and β-glucosidase. The physicochemical status of soil depended significantly on the degree of soil contamination with the herbicide, same as the yield of spring oilseed rape.     

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits,Cantabria, Spain

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ⁶⁶Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from ?0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ³⁴S?=?+6.6 and stage 2 has δ³⁴S?=??0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light ⁶⁶Zn-depleted signatures with δ⁶⁶Zn values from ?0.80 to ?0.01 per mil (mostly between ?0.80 and ?0.24 per mil) and δ³⁴S values from +10.7 to +15.7 per mil without any relationship between the δ⁶⁶Zn and δ³⁴S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250–320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH₂S?>?mZn²⁺ as a result of change in pH, T, and Zn predominant species. The light δ⁶⁶Zn accompanied by heavy δ³⁴S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ⁶⁶Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.     

New evidence of warm early-Holocene summers in subarctic Finland based on an enhanced regional chironomid-based temperature calibration model

Paleoclimate reconstructions based on biological proxies present methodological challenges, especially during non-analog conditions, such as the early Holocene. Here, two chironomid-based training sets from Finland were amalgamated to create a more accurate transfer function of summer air temperature. The aim was to reconstruct Holocene paleoclimate in northernmost Lapland, in an area that has been either too warm or too cold for reliable reconstructions using the original calibration models. The results showed that the combined calibration model had improved performance statistics. The temperature trends inferred from the downcore chironomid record using the original and combined models were very similar. However, there were major changes in their absolute values with the combined model showing greatly improved accuracy. The chironomid-based temperature reconstruction showed significant correlation with the previous pollen-based reconstructions from northwestern Finnish Lapland. However, differences were observed in the temperature trends of the early Holocene, when the chironomid-inferred temperatures rapidly increased, but the pollen-based reconstructions lagged behind suggesting that a cool climate continued for much longer. However, similar to the chironomid record, new plant macrofossil evidence from northwestern Finland also showed warmer-than-present early Holocene temperatures. Therefore, we conclude that the early Holocene was probably warm in northern Lapland.